Kinetic Studies on the Hydroformylation of 1-Hexene Using RhCl(AsPh₃)₃ as a Catalyst

Abstract

The detail kinetic study of 1-hexene hydroformylation using RhCl(AsPh3)3 as a homogeneous catalyst has been investigated. The present kinetic study involves the effect of concentrations of 1-hexene and catalyst, partial pressures of CO and H2, agitation speed, and temperature on the rate of hydroformylation. Additionally, the studies of deactivation of the catalyst RhCl(AsPh3)3 with temperature have also been done. It was observed that the rates of hydroformylation reaction were increased on increasing the initial concentrations of 1-hexene, catalyst, and partial pressures of CO and H2 at lower ranges. The activation energy was found to be 42.74 kJ/mol. A nonlinear semiempirical kinetic model was also developed to be the best fit with 11.6% error.

Hydroformylation and tandem isomerization–hydroformylation of n-decenes using a rhodium-BiPhePhos catalyst: Kinetic modeling, reaction network analysis and optimal reaction control

“…The apparent hydroformylation reaction order of CO will also shift, starting at a positive value at low CO concentrations, passing zero and ending up at a negative value at very high CO concentrations (see equation (22)). This characteristic CO hydroformylation reaction order shift was also observed experimentally in the literature using different catalysts [49][50][51][52][53][54][55]. The isomerization, however, will always have a negative apparent reaction order with respect to CO.…”

Kinetics and mechanisms of homogeneous catalytic reactions

“…B reversibly coordinates the olefin (K 2 ) to produce RhH(CO)(olefin)(dppe) (C). Then, migratory insertion of the olefin into the metal hydride bond takes place (K 3 ) with the concomitant coordination of a CO molecule to yield Rh(CO) 2 (alkyl)(dppe) (D); the reversibility of this reaction has been postulated in other works [8,15]. The insertion of CO into the Rh-alkyl bond of D, generates the unsaturated acyl species Rh(CO)(acyl)(dppe) (E) through K 4 .…”

“…In spite of the industrial importance of olefin hydroformylation and the large number of publications in this field published over several decades, relatively few studies have been devoted to the kinetics of this reaction, and most of them involve RhH(CO)(PPh 3 ) 3 [4][5][6][7][8][9]; kinetic and mechanistic studies of hydroformylation with catalysts containing bulky phosphites [10,11], phosphine-phosphite [12] or diphosphites [13], 1,2,5-triphenyl-1H-phosphole [14] and triphenylarsine [15] as ligands have also been reported. Of particular relevance to the present work, hydroformylation by rhodium-diphosphine systems has been extensively studied over the years and reasonable catalytic cycles have been proposed [1, 3,16].…”

Hydroformylation of 1-Hexene over Rh/Nano-Oxide Catalysts

“…Hydroformylation is an important industrial process for the production of both linear (n) and branched (i) aldehydes and alcohols from alkenes by CO/H 2 in the presence of a transition metal catalyst [1][2][3]. Homogeneous rhodium catalysts have been found to be highly active and selective.…”